CN109650426B - Comprehensive utilization method of waste polyaluminium chloride residue of water treatment agent - Google Patents
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Abstract
The invention provides a comprehensive utilization method of waste polyaluminium chloride slag of a water treatment agent, which comprises the step of removing Cl from the waste polyaluminium chloride slag of the water treatment agent‑Treatment to obtain dechl‑Treating fluid and mixed slurry; standing, precipitating and layering the mixed slurry to obtain bottom layer particles, middle layer particles and upper layer slurry; filter-pressing the upper layer slurry to obtain clear liquid to obtain a mud cake, mixing the mud cake with biochemical sludge and fly ash, granulating and sintering to obtain ceramsite; placing the dechlorination treatment liquid in a triple-effect four-body forced circulation evaporation device or an MVR forced circulation evaporator for carrying out circulating evaporation concentration treatment to prepare liquid polyaluminium chloride; and spraying the bottom layer particles to obtain the aluminum-containing sand. The method ensures that all components in the waste residue of the water treatment agent polyaluminium chloride are fully recycled, no new waste is discharged in the whole process, the problem of everywhere stacking pollution of the waste residue of the water treatment agent polyaluminium chloride is solved, and resource recovery is realized. The process has simple steps and is easy for industrialized popularization.
Description
Technical Field
The invention relates to the field of water purifying agents, in particular to a comprehensive utilization method of polyaluminium chloride waste residues of a water treating agent.
Background
The waste polyaluminium chloride slag of the water treatment agent is a mixture containing complex components such as aluminum, silicon, calcium, magnesium, iron, titanium and the like, and the waste slag is mostly poured and buried randomly for a long time, so that the environment risk is high. In the recent stage, environmental protection supervision is more and more strict, waste residues are not allowed to be dumped or buried any more, and the outlet of the waste residues becomes a key problem whether enterprises can survive or not.
In order to reduce the waste residue yield, enterprises usually replace the process of adding calcium aluminate and hydrochloric acid to bauxite in the original water treatment agent production process with the process of adding calcium aluminate and hydrochloric acid to aluminum hydroxide, so that the waste residue yield is greatly reduced. However, the method can not address the symptoms, and the water treatment agent polyaluminium chloride waste residue is still too large along with the accumulation of the enterprise yield. The Lina et al of the university of the China-south nationality propose that the waste residue of the water treatment agent polyaluminium chloride is treated by adopting a neutralization modification treatment method, so that the waste residue can be used as a building material to replace partial clay to prepare sintered common bricks, and can also be recycled as an additive of a decoloring agent for refining petroleum products. The patent of application No. 201610084948.9 provides a method for preparing a defluorinating agent which can be directly used in a filter column by using a sintering method to make a complex containing aluminum hydroxide in polyaluminium chloride residues and calcium silicate form a copolymer, and neutralizing the acidity in a water body to make fluoride ions and aluminum ions form stable aluminum fluoride.
However, the method has the defects that the treatment of the polyaluminum chloride waste residue by the water treatment agent is not thorough, more energy is consumed in the waste residue treatment process, new waste is generated in the treatment process and the like. Therefore, a method which can effectively solve the pollution of the polyaluminium chloride waste residue of the water treatment agent, does not generate new waste residue and can be comprehensively utilized is urgently needed in the water treatment agent industry.
In order to solve the above problems, people are always seeking an ideal technical solution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a comprehensive utilization method of polyaluminium chloride waste residues of a water treatment agent.
In order to achieve the purpose, the invention adopts the technical scheme that: a comprehensive utilization method of waste polyaluminium chloride slag of a water treatment agent specifically comprises the following steps:
dechlorination of Cl-Treating the waste polyaluminium chloride residue of water treatment agent to elute Cl-Treatment and alkali elution with alkali lye of Cl-Treatment to obtain dechl-Treating fluid and mixed slurry, wherein the mass percentage concentration of the alkali liquor is controlled8 to 15 percent;
standing and layering the mixed slurry, and performing standing, precipitation and layering treatment on the mixed slurry to obtain a mixture containing bottom layer particles, middle layer particles and upper layer slurry;
separating waste residues to sequentially separate bottom layer particles, middle layer particles and upper layer slurry from a mixture containing the bottom layer particles, the middle layer particles and the upper layer slurry; filter-pressing the upper layer slurry to obtain clear liquid to obtain a mud cake;
the classification and utilization are as follows according to the mass part ratio of (80-100): (0-20): (0-20) mixing and granulating the mud cake, biochemical sludge and fly ash according to the proportion to obtain granules to be burnt; firing the to-be-fired granules at the temperature of 1000-1300 ℃, and cooling to room temperature to obtain ceramsite; placing the dechlorination treatment liquid in a triple-effect four-body forced circulation evaporation device or an MVR forced circulation evaporator for carrying out circulating evaporation concentration treatment to prepare liquid polyaluminium chloride; and spraying the bottom layer particles to obtain the aluminum-containing sand.
Based on the above, the removal of Cl-The treatment step also comprises the substeps of firstly carrying out rough concentration and crushing on the water treatment agent polyaluminium chloride waste residue.
Based on the above, the removal of Cl-The treatment steps specifically include: firstly, roughly selecting the water treatment agent polyaluminium chloride waste residue to obtain the water treatment agent polyaluminium chloride waste residue with the particle size of more than 15mm and the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15 mm; then, a differential grinder is adopted to grind the water treatment agent polyaluminium chloride waste residue with the particle size of more than 15mm into the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15mm, and then a fluffer is utilized to sequentially carry out first water elution on the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15mm after rough separation and after grinding-Treatment and alkali elution with alkali lye of Cl-Treatment to obtain said dechl-A treatment fluid and the mixed slurry.
Based on the above, the removal of Cl-The treatment steps specifically include: said dechl-The treatment steps specifically include: firstly, the waste residue of the water treatment agent polyaluminium chloride is roughly selected to obtain the waste residue with the grain diameter of more than 15mm of waste water treatment agent polyaluminium chloride slag and waste water treatment agent polyaluminium chloride slag with the grain diameter less than 15 mm; then, a differential grinder is adopted to grind the water treatment agent polyaluminium chloride waste residue with the particle size of more than 15mm into the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15mm, and then a fluffer is utilized to sequentially carry out first water elution on the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15mm after rough separation and after grinding-Treatment and alkali washing for removing Cl-Treatment and second Water elution of Cl-Treatment to obtain said dechl-The treatment fluid, the mixed slurry and the secondary water washing fluid.
Based on the above, the removal of Cl-The treatment step also includes the substeps of recovering the second water wash and pooling it in a wash basin.
In the classification and utilization step, the removal of Cl is performed-And condensed water is also generated in the process of carrying out circulating evaporation concentration treatment on the treatment liquid, and the condensed water is recovered and collected into the washing water tank.
Based on the above, the method also comprises the step of eluting Cl by using the second water washing liquid and the condensed water which are collected into the water washing tank as the first water for the polyaluminium chloride waste residue particles of the water treatment agent-Treating the water source.
Based on the above, in the classification and utilization step, condensed water is also generated in the process of performing cyclic evaporation and concentration treatment on the dechlorination treatment liquid, and the condensed water is recycled to be used as a water source for performing spraying treatment on the bottom layer particles.
Based on the above, the classifying and utilizing step further comprises the sub-steps of stirring, molding and air-drying the middle layer particles, cement and stones to prepare the pavement bricks.
Based on the above, the alkali liquor is one or a mixture of a sodium hydroxide solution and a calcium hydroxide solution.
Compared with the prior art, the comprehensive utilization method of the water treatment agent polyaluminium chloride waste residue has outstanding substantive characteristics and obvious progress, and particularly, the comprehensive utilization method of the water treatment agent polyaluminium chloride waste residue mainly comprises the steps of firstly removing Cl from the water treatment agent polyaluminium chloride waste residue-Processing to obtain dechlorination treatment liquid and mixed slurry; then carrying out circulating evaporation concentration treatment on the dechlorination treatment liquid to obtain a liquid polyaluminium chloride finished product; standing, precipitating and layering the mixed slurry to obtain bottom layer particles, middle layer particles and upper layer slurry; and sequentially separating the bottom layer particles, the middle layer particles and the upper layer slurry to prepare ceramsite, pavement bricks and aluminum-containing sand respectively. By the method, all components in the waste residue of the water treatment agent polyaluminium chloride are fully recycled, the waste residue of the water treatment agent polyaluminium chloride is free from residue, waste is changed into valuable, and no new waste is generated in the waste residue treatment process, so that the problem that the waste residue of the water treatment agent polyaluminium chloride is piled everywhere to pollute the environment is solved, the resource recycling is realized, and the process is simple in step, green and environment-friendly and easy for industrial popularization.
Further, the method removes Cl from the waste residue of the polyaluminium chloride of the water treatment agent-During treatment, the water treatment agent polyaluminium chloride is easy to dissolve in water, and water and alkali liquor are adopted to remove Cl-Treatment, essentially purely physical dechlorination-The method does not need to consume a heat source and can dissolve and recover the residual polyaluminium chloride in the polyaluminium chloride waste residue of the water treatment agent to the maximum extent. Meanwhile, the invention uses the alkali liquor with the mass percentage concentration of 8-15% to carry out alkali elution on the polyaluminium chloride waste residue of the water treatment agent to remove Cl-Treatment while ensuring dechlorination-And meanwhile, the influence of the high-concentration alkali liquor on the subsequent recovery of the liquid polyaluminium chloride is reduced.
Furthermore, the biochemical sludge, the fly ash and other raw materials selected in the preparation of the ceramsite by the method are solid wastes, no new resource needs to be additionally added, and the purpose of treating wastes with processes of wastes against one another is completely realized.
Further, the method also comprises the step of respectively recovering the water washing liquid in the second water washing treatment and the condensed water in the circulating evaporation and concentration treatment of the dechlorination treatment liquid, and eluting Cl by using the water washing liquid and the condensed water as first water-Treating the water source. This step is carried out with increasing the dechlorination-The effect, the dechlorination effect of the polyaluminium chloride waste residue of the water treatment agent is more thorough, the water resource is saved, the cost is reduced, and the dechlorination effect of the polyaluminium chloride waste residue of the water treatment agent is realizedAnd (4) recycling the resources.
Furthermore, the method also comprises the steps of crushing the water treatment agent polyaluminium chloride waste residue by utilizing the differential crusher, fully utilizing the rotation speed difference between two crushing rollers in the differential crusher, artificially strengthening the slip phenomenon in the crushing process, prolonging the contact and detention time between the water treatment agent polyaluminium chloride waste residue and crushing teeth of the crushing rollers, overcoming the slip phenomenon of the water treatment agent polyaluminium chloride waste residue during crushing, enabling the whole crushing process to be more perfect and effective, shortening the crushing time and increasing the particle surface area, enabling the water treatment agent polyaluminium chloride waste residue particles to be fully contacted with water and alkali liquor, accelerating the water washing and alkali washing processes, and shortening the dechlorination treatment time. Meanwhile, the method adopts a fluffing device to sequentially carry out first water elution on the crushed, screened and screened water treatment agent polyaluminium chloride waste residue particles to elute Cl-Treatment and alkali washing for removing Cl-Treatment and second Water elution of Cl-The treatment ensures that the water treatment agent polyaluminium chloride waste residue particles can be fully stirred and mixed with the water washing liquid and the alkali liquor, accelerates the water washing and alkali washing processes, and shortens the Cl removal-And (4) processing time.
Further, the method also comprises the step of removing Cl from the polyaluminium chloride waste residue of the water treatment agent by utilizing a triple-effect quadruple forced circulation evaporation device or an MVR forced circulation evaporator-The treatment liquid is subjected to forced circulation, evaporation and concentration, and the Cl removal from the polyaluminium chloride waste residue of the water treatment agent is ensured-The polyaluminum chloride recovered from the treatment solution has uniform components, uniform heating and stable performance.
Furthermore, the method continuously washes the bottom layer particles by using fine liquid sprayed by spraying equipment through spraying treatment on the bottom layer particles, so that the contact area between the particles and the liquid is increased, and the impurity content of the prepared aluminum-containing sand is reduced.
Drawings
FIG. 1 is a process flow diagram of a comprehensive utilization method of waste polyaluminium chloride slag as a water treatment agent provided in embodiment 1 of the invention.
FIG. 2 is a process flow diagram of a comprehensive utilization method of waste polyaluminium chloride slag as a water treatment agent provided in embodiment 2 of the invention.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments.
In each of the following examples, waste polyaluminium chloride slag, which is a conventional water treatment agent in the market, was used as a treatment target.
Henan consolidates the biggest base for producing water purifying agents in China, and the yield of the water purifying agents accounts for more than 60% of the whole country and reaches 120 ten thousand tons per year. Because most manufacturers produce bauxite + calcium aluminate + hydrochloric acid, millions of tons of wet-based waste slag are produced each year. In the past, most of waste residues of water purifying agents are poured and buried randomly, which causes serious waste pollution. With the increasing environmental protection requirement, how to realize harmless treatment of the polyaluminum chloride waste residue of the water treatment agent is a bottleneck for restricting the development of the water purification agent industry.
The chemical components of 8 samples selected by experimental analysis of the polyaluminium chloride waste residue of the existing water treatment agent in the consolidation market are shown in table 1, and as can be seen from table 1, the polyaluminium chloride waste residue of the existing water treatment agent in the consolidation market has similar chemical components and contains water with the average mass percent of 22.05 percent and Al with the average mass percent of 22.31 percent2O338.9% of SiO21.97% of TiO20.39% of MgO, 3.04% of CaO, 1.74% of Fe2O3。
TABLE 1 Water treatment agent polyaluminium chloride waste residue chemical composition table
| Sample number | Water content% | Al2O3％ | SiO2％ | TiO2％ | MgO％ | CaO％ | Fe2O3％ |
| 1 | 33 | 15.61 | 37.12 | 1.82 | 0.15 | 1.88 | 1.21 |
| 2 | 31.62 | 17.92 | 29.17 | 2.59 | 0.63 | 3.46 | 2.5 |
| 3 | 26.8 | 24.4 | 40.92 | 1.5 | 0.4 | 3.78 | 1.5 |
| 4 | 8 | 25.6 | 41.7 | ||||
| 5 | 10 | 28.12 | 43.92 | ||||
| 6 | 15.56 | 26.01 | 39.72 | ||||
| 7 | 22.58 | 21.04 | 36.46 | ||||
| 8 | 28.86 | 19.76 | 42.15 | ||||
| Mean value | 22.05 | 22.31 | 38.90 | 1.97 | 0.39 | 1.74 |
Example 1
The embodiment provides a comprehensive utilization method of waste polyaluminium chloride slag as a water treatment agent, and specifically, a flow chart of the method is shown in fig. 1, and the method specifically comprises the following steps:
dechlorination of Cl-The treatment comprises the steps of sequentially eluting Cl with first water from the waste residue of polyaluminium chloride of water treatment agent by using a fluffing device-Treatment and alkaline elutionCl-Treatment to obtain dechl-Treating liquid and mixed slurry, wherein the mass percentage concentration of alkali liquor used in the alkali washing is controlled to be 10%, and the alkali liquor is sodium hydroxide solution; first elution of Cl with water-Treatment and alkaline elution to remove Cl-When in treatment, the water treatment agent polyaluminium chloride waste residue mud blocks on the hydrapulper are completely dispersed and can be kept stand for layering; the fluffing device is a hydraulic pulper;
standing and layering the mixed slurry, and performing standing, precipitation and layering treatment on the mixed slurry to obtain a mixture containing bottom layer particles, middle layer particles and upper layer slurry;
separating waste residues to sequentially separate bottom layer particles, middle layer particles and upper layer slurry from a mixture containing the bottom layer particles, the middle layer particles and the upper layer slurry; filter-pressing the upper layer slurry to obtain clear liquid to obtain a mud cake;
the classification and utilization are carried out according to the mass part ratio of 80: 10: 13, mixing and granulating the mud cake, biochemical sludge and fly ash to obtain granules to be burned, burning the granules to be burned at the temperature of 1100 ℃, and cooling to room temperature to obtain ceramsite; placing the dechlorination treatment liquid in a triple-effect four-body forced circulation evaporation device for carrying out circulation evaporation concentration treatment to obtain the product containing 30% Al2O3The liquid polyaluminium chloride finished product is obtained; and (3) placing the bottom layer particles in spraying equipment, and spraying the bottom layer particles for 50min by using water as a spraying medium to obtain the aluminum-containing sand.
Example 2
The embodiment provides a comprehensive utilization method of waste polyaluminium chloride slag as a water treatment agent, and the flow chart of the method is shown in figure 2, and the method specifically comprises the following steps:
dechlorination of Cl-Firstly, carrying out rough concentration on the water treatment agent polyaluminium chloride waste residue to obtain the water treatment agent polyaluminium chloride waste residue with the particle size of more than 15mm and the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15 mm; adopting a differential grinder to grind the water treatment agent polyaluminium chloride waste residue with the particle size of more than 15mm into the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15mm, and then utilizing a fluffer to coarsely select the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15mm15mm of water treatment agent polyaluminium chloride waste residue is sequentially subjected to first water elution for Cl-Treatment and alkali washing for removing Cl-Treatment and second Water elution of Cl-Treatment to obtain dechl-The treatment solution, the mixed slurry and a second water washing solution, wherein the mass percentage concentration of an alkali liquor used in the alkali washing is controlled to be 13%, and the alkali liquor is a calcium hydroxide solution;
standing and layering the mixed slurry, and performing standing, precipitation and layering treatment on the mixed slurry to obtain a mixture containing bottom layer particles, middle layer particles and upper layer slurry;
separating waste residues to sequentially separate bottom layer particles, middle layer particles and upper layer slurry from a mixture containing the bottom layer particles, the middle layer particles and the upper layer slurry; filter-pressing the upper layer slurry to obtain clear liquid to obtain a mud cake;
the classification and utilization are as follows according to the mass part ratio of 100: 20: 16, mixing and granulating the mud cake, the biochemical sludge and the fly ash to obtain granules to be burnt, burning the granules to be burnt at the temperature of 1200 ℃, and cooling to room temperature to obtain ceramsite; placing the dechlorination treatment liquid in MVR forced circulation evaporator equipment for cyclic evaporation and concentration treatment to obtain the product containing 30% Al2O3The liquid polyaluminium chloride finished product is obtained; and (3) placing the bottom layer particles in spraying equipment, and spraying the bottom layer particles for 50min by using water as a spraying medium to obtain the aluminum-containing sand.
In order to recycle resources, the water treatment agent polyaluminium chloride waste residue comprehensive utilization method provided by the embodiment recovers the secondary water washing solution and collects the secondary water washing solution into a water washing pool; and recovering said dechl-Condensed water generated when the treatment solution is subjected to circulating evaporation concentration treatment is collected into the washing water tank; then the second water washing liquid and the condensed water which are converged into the water washing tank are used as first water for eluting Cl from the polyaluminium chloride waste residue particles of the water treatment agent-Treating the water source.
And simultaneously, the condensed water generated when the dechlorination treatment liquid is subjected to circulating evaporation concentration treatment can also be used as a water source for performing cyclic utilization when the bottom-layer particles are subjected to spraying treatment.
Example 3
The embodiment provides a comprehensive utilization method of waste polyaluminium chloride slag as a water treatment agent, which has the same steps as those in the embodiment 2, and is different from the following steps: the mass part ratio of the mud cake to the biochemical sludge to the fly ash is 17: 2: 1.
the biochemical sludge used as the raw material for preparing the ceramsite in each embodiment is derived from municipal sludge in the consolidated market, and the sludge contains a large amount of organic matters, so that a large amount of pores are formed after high-temperature carbonization, and the production of the ceramsite is facilitated. In addition, the sludge has a certain calorific value, so that the fuel consumption in the firing process is reduced, and the purposes of easily obtaining local materials on raw materials and treating waste by waste in the comprehensive utilization method of the water treatment agent polyaluminium chloride waste residue are realized.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those of ordinary skill in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (5)
1. A comprehensive utilization method of waste polyaluminium chloride slag of a water treatment agent specifically comprises the following steps:
dechlorination of Cl-Firstly, roughly selecting the waste water treatment agent polyaluminium chloride slag to obtain the waste water treatment agent polyaluminium chloride slag with the grain size of more than 15mm and the waste water treatment agent polyaluminium chloride slag with the grain size of less than 15 mm; then, a differential grinder is adopted to grind the water treatment agent polyaluminium chloride waste residue with the particle size of more than 15mm into the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15mm, and then a fluffer is utilized to sequentially carry out first water elution on the water treatment agent polyaluminium chloride waste residue with the particle size of less than 15mm after rough separation and after grinding-Treatment and alkali washing for removing Cl-Treatment and second Water elution of Cl-Treatment to obtain dechl-Treating fluid, mixed slurry and secondary washing fluid; recovering the secondary water washing liquid and collecting the secondary water washing liquid into a water washing pool, wherein the mass percentage concentration of the alkali liquor is controlled to be 8-15%;
standing and layering the mixed slurry, and performing standing, precipitation and layering treatment on the mixed slurry to obtain a mixture containing bottom layer particles, middle layer particles and upper layer slurry;
separating waste residues to sequentially separate bottom layer particles, middle layer particles and upper layer slurry from a mixture containing the bottom layer particles, the middle layer particles and the upper layer slurry; filter-pressing the upper layer slurry to obtain clear liquid to obtain a mud cake;
the classification and utilization are as follows according to the mass part ratio of (80-100): (0-20): (0-20) mixing and granulating the mud cake, biochemical sludge and fly ash according to the proportion to obtain granules to be burnt; firing the to-be-fired granules at the temperature of 1000-1300 ℃, and cooling to room temperature to obtain ceramsite; placing the dechlorination treatment liquid in a triple-effect four-body forced circulation evaporation device or an MVR forced circulation evaporator for carrying out circulating evaporation concentration treatment to prepare liquid polyaluminium chloride; spraying the bottom layer particles to obtain aluminum-containing sand; and stirring, molding and air-drying the middle layer particles, cement and stones to prepare the pavement brick.
2. The method for comprehensively utilizing waste residues of water treatment agent polyaluminum chloride according to claim 1, wherein in the classifying and utilizing step, the dechl is performed-And condensed water is also generated in the process of carrying out circulating evaporation concentration treatment on the treatment liquid, and the condensed water is recovered and collected into the washing water tank.
3. The comprehensive utilization method of water treatment agent polyaluminium chloride waste residue as claimed in claim 2, further comprising eluting Cl with the second water washing solution and the condensed water collected in the water washing tank as the first water for the water treatment agent polyaluminium chloride waste residue particles-Water source.
4. The method for comprehensively utilizing waste residues of water treatment agent polyaluminum chloride according to claim 3, wherein in the classifying and utilizing step, the dechl is performed-And condensed water is also generated in the process of carrying out circulating evaporation concentration treatment on the treatment solution, and the condensed water is recovered to be used as a water source for carrying out spraying treatment on the bottom-layer particles.
5. The comprehensive utilization method of water treatment agent polyaluminium chloride waste residues as claimed in any one of claims 1 to 4, wherein the alkali solution is one or a mixture of a sodium hydroxide solution and a calcium hydroxide solution.
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| CN112108504A (en) * | 2020-09-28 | 2020-12-22 | 成都庶民科技有限公司 | Industrial waste residue recycling device and method |
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| CN101492271A (en) * | 2008-12-10 | 2009-07-29 | 乔占印 | Method for producing construction brick with industrial residue |
| CN207072810U (en) * | 2017-05-13 | 2018-03-06 | 江苏蓝遥净水剂有限公司 | A kind of aluminium polychloride produces waste residue recycle device |
| CN108585934A (en) * | 2018-06-25 | 2018-09-28 | 西安科技大学 | A kind of aluminium sludge ceramsite preparation method |
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